Process of imparting hydrophobic properties to cellulose fibers



Patented July 11, 1939 UNITED STATES PROCESS OF IMPARTING HYDROPI IOBICPROPERTIES T CELLULOSE FIBERS Franz Emil, Hubert, Dessau-Zlebigk, ErwinHeisenberg, LcipIlI, and Adolf Steindoril. and Ludwig ortlincr,Frankfort-on-the-Maln,

Ger-

many, assignors to I. G. Farbenindustrie Aktlengesellschait, Frankforton-the-Main, Germany No Drawing. Application May 21,- 1936, Serial 7 No.81,122. In Germany May 11, 1935;

Claims.. (Cl. 91'l0) The present invention relates to a process ofimparting hydrophobic properties to cellulose fibers.

It is known that fibers of cellulose or hydrated 5 cellulose, such ascotton, artificial silk or staple fiber are extraordinarily hydrophil,that is to say they are very quickly wetted when in contact with water.This property is a great disadvantage for many of the applications ofthis material.

This invention consists in a process for making cellulose fibershydrophobe by applying to the fibers or incorporating with them acompound which contains at least one aliphatic or cycloaliphatic residuehaving at least 4 carbon atoms and capable of reacting with aldehyde andexposing the fibers thus treated simultaneously or subsequently to theaction of an aliphatic aldehyde or dialdehyde, for instance,formaldehyde or glyoxal.

v Suitable aliphatic compounds are, for example,

fatty amines and fatty acid amides such as dodecylamine, hexadecylamine,octadecenylamine, abietic acid amide, lauric acid amide,stearoyl-methylamide, stearoyl-butylamide, stearoyloctadecylamide;further compounds of the character of alkyl-substituted ureas having thegeneral formula:

/H R.X.CO.N

wherein R. stands for a radical selected from the group consisting ofaliphatic and cycloaliphatic radicals containing at least 4 carbonatoms, X 35 stands for a member selected from the group consisting of O,NH, N. alkyl, and R1 stands for a member of the group consisting ofhydrogen and aliphatic hydrocarbon radicals, such as mono-isobutyl urea,monododecyl urea, monooctadecyl urea, stearoyl urea; further fatty acidimino ethers or arnidines. There also come into consideration compoundscontaining hydroxyl groups, such as, for instance, dodecylphenol,diisohexyl-phenol. Instead of the products named above there may also beused with advantage their products of reaction with aliphatic aldehydes,for example, their methylol compounds. If these latter are used theseparate after-treatment with formaldehyde can be omitted in many 50cases, a simple after-heating operation sufiicing. The process may beconducted, for example,

as follows: .the cellulose fibers are first saturated with a solution ofthe aliphatic compound in an organic solvent, for instance, pyridine, oracetone 55 or in an aqueous emulsion of the aliphatic compounds. Theyare then dried and exposed to the atcion of, for instance, formaldehyde,the concentration of which, when it is used in the form of a solution,must not be more than 5%. The formaldehyde may be added to theimpregnating solution so that a subsequent treatment with formaldehydebecomes unnecessary; however, care must likewise be taken that theconcentration of the aldehyde, for instance, of the formaldehyde, in thetreating solution is not more than 5%. In this case the fiber needs onlysubsequent heating to ensure sufiicient reaction of the formaldehydewith the impregnating compound and the fiber.

In many cases it is useful to conduct the subsequent heating in an acidmedium. For this purpose there may be added, for example, to the aqueousemulsion, acetic acid, lactic acid or agents of acid reaction such' assodium bisulfite.

Fibers treated in this manner are characterized by a particularly highstability towards-water and even hot soap solution. For example, suchmaterial can be subjected to the usual fulling treatment, that is to sayheating for A; hour in a. solution of 50 grams of soap and 5 grams ofsodium carbonate per liter at 50 C. without loss of the property ofrepellent water. By suitable combination of the parent material andworking conditions an effect can be obtained which is not notablydiminished by several washings with boiling soap solution.

Another process of rendering cellulose fibers water-repellent consistsin treating the fibers with solutions or dispersions of the aldehydecondensation products. As;a catalyst an acid substance is suitably addedto the solutions or dispersions. The fibers may also be pretreatedwithan acid substance. The said aldehyde condensation products may alsobe added directly to the spinning solutions from which the artificalcellulose threads are prepared. The fibers which are prepared fromsolutions containing such an addition may, if required, be treatedsubsequently with an aldehyde.

The following examples serve to illustrate the invention, but they arenot intended to limit it thereto; the parts are by weight:

1. Unsoaped dry viscose silk is immersed for 5 minutes in 5 times itsweight of 'a pyridine solution containing 5-10 pen cent. ofoctadecylhepadecyl urea of the formula:

The silk is then drained, dried, immersed for 5 minutes in aqueousformaldehyde solution of 30 per cent. strength, centrifuged, dried andheated for 16 hours at C. Instead of this treatment with formaldehydethe fibrous material may be suspended for hour in a chamber charged withformaldehyde vapor at C. Instead of octadecyl-heptadecyl urea another ofthe substances specified above may be used.

2. Unsoaped dry viscose silk is immersed for 5 minutes in 10 times itsweight of an aqueous emulsion containing 2 per cent. of stearin-amide,0.2 per cent. of an emulsifying agent, obtainable by the reaction ofethylene-oxide with octadecenyl-alcohol, and0.3 per cent. offormaldehyde. The goods are centrifuged, dried and heated for 6 hours at110 C. A subsequent washing is not necessary.

3. Unsoaped, dry viscose silk is immersed for 5 minutes in 5 times itsweight of a solution of 5-10 per cent. strength of methylol-stearinamidein pyridine. The goods are centrifuged, dried and heated for 15 hours at110 C.

4 The operation is conducted as described in Example 2 but 7 per cent.of lactic acid is added to the emulsion. By this addition of acid thestability of the water repelling preparation is strongly increased,particularly towards treatment with boiling dilute acid.

5. 10 parts of monostearylamino-cyanuric diamide are dissolved bywarming 50 parts of a 10% lactic acid solution until the mass ishomogeneous. The whole is made up with water to 2000 parts and whilestirring, 40 parts of formaldehyde of 40 per cent. strength are added. Aviscose artificial silk fabric is impregnated with this solution,squeezed, dried at moderate temperature and thereupon heated for 15minutes at 155 C. to 160 C. The tissue thus treated is verywater-repellent even after the usual washing with soap.

A similar good effect is also obtained by causing other aminoderivatives of the 1.3.5-triazine, containing an alkyl radical with atleast 4 carbon atoms, to act upon the cellulose fibers and "treatingthem, either simultaneously or subsequently, with aliphatic aldehydes.For example the 1.3.5-triazine of the formula:

obtainable from monochlorcyanuric diamide andl-amino-2-stearylamino-ethane, is a substance of good activity.

6. Dry viscose artificial silk is treated for 15 minutes with a solutionof 5 grams of a condensation product, obtainable from stearic acid amideand aqueous formaldehyde, in 1 liter of carbon tetrachloride. Thematerial is squeezed and dried in the air. Thereupon it is aftertreatedat room temperature for 15 minutes with [I a solution of 5 grams oflactic acid in 1 liter of water, squeezed, dried in a current of air andheated for 2 hours at 110 C. The material is finally well rinsed anddried.

7. Viscose artificial silk tissue is treated for 10 minutes with anaqueous solution of the sodium salt of stearyl aminomethanesulfonic acidor stearylmethylaminomethanesulfonic acid, 5 grams of lactic acid beingadded per liter. The material is squeezed and dried at a temperature of40 C. to 50 C. The tissue is then heated for 5-10 minutes at atemperature of C. to C.

8.'Undyed or dyed viscose artificial silk is treated with a solutionwhich contains per liter of water 5 grams of lactic acid or glycolicacid, and is then dried. This pretreated material is treated for 10minutes at 60 C. to 70 C. with a solution of a condensation product,obtainable from montanic acid amide and aqueous formaldehyde, in carbontetrachloride. The material is squeezed, dried and heated for someminutes at a temperature of 140 C. There is thus obtained a hydrophobetissue having a very good waterrepellent effect.

9. 4 parts of viscose artificial silk are impregnated with 100 parts byvolume of a 1 per cent. solution of dodecylvinylether in dioxane,squeezed and dried. The silk is then loosened and heated for 2 hours at110 C. under reduced pressure in an atmosphere of glacial acetic acidand formaldehyde. Thereupon it is washed while cold, hydro-extracted anddried. The viscose silk is very water-repellent and resistant toboiling.

10. Dyed viscose artificial silk fabric is 'immersed in a 2 per cent.solution of carbamic acidoctadecyl ester having the formula:

C1aH37.O.CO.NH2

in methylene chloride for about 10 minutes, then squeezed and afterevaporation of the solvent the material is conducted through a bathwhich contains 5 per cent. of formaldehyde and 0.5 per cent. of la'cticvacid. The material is then dried in a tentering frame for abouthalf-an-hour at 105 C. to 110C. Even after washing with soap thematerial is water-repellent and impermeable to water.

Instead of viscose artificial silk, cellulose fibers of all kinds, forinstance, copper artificial silk, artificial spinning fibers, cotton,also mixtures of wool and cellulose fibers as well as fabrics made fromthe said fibers and mixtures of fibers may be used. In some cases apreliminary cleansing or desizing of the fibers or fabric is advisable.

' We claim:

1. The process of imparting hydrophobic properties to cellulose fibersby impregnating the fibers in a bath which contains compounds of thegeneral formula:

' f, wherein R star ids for a radical selected from the group consistingof aliphatic and ,cycloali phatic radicals containing at least 4 carbonatoms, X stands for a member selected from the group consisting of O,NH, N.alkyl and R1 stands for a member of the group consisting ofhydrogen and, aliphatic hydrocarbon radicals, at most 5 per cent. ofaldehyde and an agent of acid action, and heating them after theimpregnation.

3. The process of imparting hydrophobic properties to cellulose fibersby incorporating with them a compound of the general formula:

wherein R stands for a radical selected from the group consisting ofaliphatic and cycloaliphatic radicals, containing at least '4 carbonatoms, x

stands for a radical selected from the group consisting of O, NH,N.alkyl and R1 stands for a member of the group consisting of hydrogenand aliphatic hydrocarbon radicals, treating the fibers with aliphaticaldehydes and subsequently heating them.

4. The process of imparting hydrophobic properties to cellulose fibersby impregnating the fibers with a condensation product from an aldehydeand a compound of the general formula:

wherein R stands for a radical selected from the group consisting ofaliphatic and cycloaliphatic radicals containing at least 4 carbonatoms,'X

wherein R stands for a radical selected from the group consisting ofaliphatic and cycloaliphatic radicals containing at least 4 carbonatoms, X stands for a radical selected from the group consisting of 0,NH, N.alky1 and R1 stands for a member of the group consisting ofhydrogen and aliphatic hydrocarbon radicals, in the presence of an agentof acid action, and heating them after the impregnation.

- FRANZ EMIL HUBERT.

ERWIN HEISENBERG. ADOLF STEINDORFI". LUDWIG ORTHNER.

